JP7846521B2 - Anti-icing and anti-snow emulsion composition - Google Patents

Description

This invention relates to an emulsified composition for ice and snow protection. More specifically, it relates to an emulsified composition for ice and snow protection containing modified cellulose fibers having a specific structure.

In heavy snowfall areas, traffic accidents occur due to snow accumulating on road signs and traffic lights. Furthermore, the arduous task of removing snow from roofs places a significant burden on residents, and tragic accidents and problems caused by falling snow onto neighboring houses are major issues. In addition, snowfall presents environmental challenges, such as reduced power generation efficiency due to snow accumulation on solar panels.
For this reason, the development of paints with snow-repellent properties is progressing. For example, Patent Document 1 describes a coating film formed by drying an organic solvent-based paint containing an oxidative-curable resin and a fluorine-based surfactant, which provides a long-lasting snow-sliding effect.

On the other hand, there are known techniques for making objects slide by creating a surface with a porous structure that retains oil. For example, Patent Document 2 discloses that a surface with a rough surface (a fine uneven structure) that retains lubricating oil has a high effect in suppressing ice adhesion.

Japanese Patent Publication No. 2016-169384 Special Publication No. 2014-509959

The snow-preventive coating described in Patent Document 1 has a hydrophilic surface, which means that it may not be sufficiently effective unless some of the snow on the coating surface melts and forms a water film. Furthermore, there is a concern that if the water film freezes on the surface due to a drop in temperature, its performance may deteriorate.

Furthermore, while the surface described in Patent Document 2, which retains lubricating oil in an uneven structure, exhibits a certain degree of anti-icing effect, its durability is insufficient, and there are concerns that its performance will deteriorate if it is damaged or if the lubricating oil is depleted.

Therefore, the object of the present invention is to provide a composition that can slide off ice and snow regardless of changes in ambient temperature, and that can form a highly durable film that exhibits this effect over a long period of time.

The present invention relates to the following [1] to [3].
[1] An emulsified composition for ice and snow protection containing the following components (A) to (C).
(A) One or more modified cellulose fibers selected from the group consisting of the following components (a) and (b).
(a) Anionic modified cellulose fibers having a type I crystal structure
(b) Hydrophobic modified cellulose fiber having a type I crystalline structure, wherein a modifying group is bonded to one or more groups selected from the group consisting of anionic groups and hydroxyl groups. (B) Water (C) Organic compound that is liquid at 25°C and 1 atm [2] A method for producing an anti-icing and anti-snow film, comprising the steps of applying and drying the anti-icing and anti-snow emulsifying composition described in [1] above.
[3] A structure obtained by drying the anti-ice and anti-snow emulsified composition described in [1] above and forming a coating film.

According to the present invention, it is possible to provide a composition that can form a film capable of effectively sliding off ice and snow adhering to various substrates.

1. Emulsified composition for ice and snow protection The emulsified composition for ice and snow protection of the present invention contains the following components (A) to (C).
In this specification, "for ice and snow protection" means at least one of the uses of ice protection and snow protection, preferably both uses.

<Ingredients (A)>
Component (A) is one or more modified cellulose fibers selected from the group consisting of components (a) and (b) below.
(a) Anionic modified cellulose fibers having a type I crystal structure
(b) Hydrophobic modified cellulose fiber having a type I crystalline structure, wherein a modifying group is attached to one or more groups selected from the group consisting of anionic groups and hydroxyl groups.

In this specification, modified cellulose fibers refer to component (a) or component (b).

[Average fiber diameter of modified cellulose fibers]
From the viewpoint of ease of handling, the average fiber diameter of the modified cellulose fibers is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more. From the viewpoint of strength when the film is formed, it is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. The average fiber diameter of the modified cellulose fibers is measured by the method described in the examples below.

[Anionic modified cellulose fiber (a)]
The anionically modified cellulose fibers used in this invention are cellulose fibers that have been anionically modified to contain anionic groups within the cellulose fibers.

Anion-modified cellulose fibers have a cellulose type I crystalline structure. From the viewpoint of strength development during film formation, the crystallinity of the anion-modified cellulose fibers is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. Furthermore, from the viewpoint of raw material availability, it is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less. In this specification, the crystallinity of various cellulose fibers refers to the cellulose type I crystallinity calculated from the diffraction intensity value by X-ray diffraction, and can be measured according to the method described in the examples below. Cellulose type I refers to the crystalline form of natural cellulose, and cellulose type I crystallinity refers to the proportion of the crystalline region within the entire cellulose fiber. The presence or absence of a cellulose type I crystalline structure can be determined by the presence of a peak at 2θ = 22.6° in X-ray diffraction measurement.

Anionic groups contained in anionically modified cellulose fibers include, for example, carboxyl groups, sulfonic acid groups, and phosphate groups. From the viewpoint of the efficiency of introducing modifying groups into cellulose fibers, carboxyl groups are preferred. Examples of counterions to the anionic groups in anionically modified cellulose fibers include metal ions such as sodium ions, potassium ions, calcium ions, and aluminum ions, which are generated in the presence of alkali during manufacturing, and protons, which are generated by substituting these metal ions with acid.

The anionic group content in anionically modified cellulose fibers is preferably 0.1 mmol/g or more, more preferably 0.4 mmol/g or more, even more preferably 0.6 mmol/g or more, and even more preferably 0.8 mmol/g or more, from the viewpoint of introducing modifying groups. Furthermore, from the viewpoint of improving handling properties, it is preferably 3 mmol/g or less, more preferably 2 mmol/g or less, and even more preferably 1.8 mmol/g or less. Note that "anionic group content" refers to the total amount of anionic groups in the cellulose constituting the cellulose fiber, and is specifically measured by the method described in the examples below.

From the viewpoint of handling ease, the average fiber diameter of the anion-modified cellulose fibers is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more. From the viewpoint of film strength, it is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. The average fiber diameter of the anion-modified cellulose fibers is measured by the method described in the examples below.

As anionically modified cellulose fibers, carboxyl-containing cellulose fibers, where the anionic group is a carboxyl group, are more preferred from the viewpoint of ease of preparation and mild reaction conditions.

[Hydrophobic modified cellulose fibers (b)]
The hydrophobic modified cellulose fiber of component (b) has a modifying group attached to a specific group of anionic modified cellulose fiber having a type I crystal structure. The attachment site for the modifying group is one or more groups selected from the group consisting of anionic groups and hydroxyl groups.

When the aforementioned bonding site is a hydroxyl group of anionically modified cellulose fiber, the bonding mode is covalent, and examples include ether bonds, ester bonds, and carbonate bonds.

When the aforementioned bonding site is an anionic group of anion-modified cellulose fiber, the bonding mode is either ionic or covalent. In the case of ionic bonding, the modifying compound having a cationic group is bonded via electrostatic interaction. In the case of covalent bonding, it refers to bonding via ester bonds, amide bonds, etc., and in particular, to the carboxyl groups of carboxyl group-containing cellulose fibers, it refers to bonding via ester bonds, amide bonds, carbonate bonds, urethane bonds, etc.

For example, if the compound used to introduce the modifying group (referred to as the "modifying compound" in this specification) is a polymer compound, such as an amino-modified silicone (referred to as " _H₂N- [alkylsilicone skeleton]"), and the anionic-modified cellulose fiber is a carboxyl group-containing cellulose fiber (referred to as "[cellulose skeleton] ^-C₆ (=O)-OH"), then if the bonding mode is an ionic bond, the hydrophobic-modified cellulose fiber will have a structure like "[cellulose skeleton] ^-C₆ (=O)-O- _H₃N ⁺ -[alkylsilicone skeleton]", and the modifying group will be "-[alkylsilicone skeleton]". On the other hand, if the bonding mode is an amide bond, the hydrophobic-modified cellulose fiber will have a structure like "[cellulose skeleton] ^-C₆ (=O)-NH-[alkylsilicone skeleton]", and the modifying group will be "-[alkylsilicone skeleton]". Thus, the structure of the modifying group depends on the structure of the modifying compound used. Note that " ^C₆ " refers to the carbon atom at position 6 of the cellulose constituent unit.

One preferred embodiment of the hydrophobic modified cellulose fiber of component (b), that is, the hydrophobic modified cellulose fiber formed by bonding a polymer compound to a cellulose fiber, has a structure represented by the following general formula (T-Ce).

(In the formula, X is one or more groups selected from the group consisting of _-CH₂OH , _-CH₂O - ^R₁ , -C(=O)OH, -C(=O)O- ^R₁ , -C(=O)-O ^- _H₃N⁺ - ^R₁ , and -C(=O)-NH- ^R₁ , where ^R₁ is a modifying group, and R is independently a hydrogen atom or a modifying group, and ^R₁ and R may be the same or different, and at least one of the multiple ^R₁ and R is a modifying group. m is an integer between 20 and 3,000.)

In hydrophobic modified cellulose fibers, which are formed by bonding a polymer compound to an anionic modified cellulose fiber having a type I crystalline structure, the modifying groups are derived from the polymer compound, and the structure of the modifying groups (i.e., ^R1 and R in the formula (T-Ce)) depends on the structure of the polymer compound used. The mode of bonding of the modifying groups to the cellulose fibers is preferably covalent or ionic. From the viewpoint of ease of manufacture, ionic bonding is preferred, and from the viewpoint of the stability of the formed film, covalent bonding is preferred.

Furthermore, examples of modifying compounds include hydrocarbon compounds having cationic groups. In hydrophobic modified cellulose fibers formed by the ionic bonding of such hydrocarbon compounds, the modifying groups are preferably derived from hydrocarbon compounds having cationic groups, for example, those with a total of 16 to 40 carbon atoms. In this case, the mode of bonding of the modifying group to the anionic groups of the anionic modified cellulose fiber is ionic, and the hydrophobic modified cellulose fiber is in a state where the cationic groups of the modifying group are adsorbed to the anionic groups on the surface of the anionic modified cellulose fiber via electrostatic interactions.

The inventors have discovered that by coating a substrate with a hydrophobic-modified cellulose fiber (in which a polymer compound or a specific hydrocarbon compound is bonded to cellulose fibers) and an emulsion composition containing water and an organic compound that is liquid at 25°C and 1 atm, and then drying it, it is possible to unexpectedly produce a film with high ice-sliding and snow-sliding properties, regardless of changes in ambient temperature, and with excellent durability. While the mechanism by which this effect occurs is not entirely clear, it is presumed that in the emulsion composition, the hydrophobic-modified cellulose fibers form particulate structures containing the organic compound that is liquid at 25°C and 1 atm, and that these particulate structures layer and form a film upon drying. The film thus formed is thought to be highly durable because, due to the mobility of the lubricating oil held in the particulate structure, ice and snow can slide off even without melting, and the particulate structure firmly holds the lubricating oil.

The amount of modifying groups (mol/g) and the introduction rate (mol%) in hydrophobic modified cellulose fibers refer to the amount and proportion of modifying groups introduced into the hydrophobic modified cellulose fibers. The amount and introduction rate of modifying groups can be adjusted by the amount and type of modifying compound added, the reaction temperature, reaction time, and solvent.

From the viewpoint of obtaining a film with improved ice and snow resistance, the amount of modifying groups attached to the hydrophobic modified cellulose fibers is preferably 0.1 mmol/g or more, more preferably 0.2 mmol/g or more, and even more preferably 0.5 mmol/g or more. Furthermore, from the viewpoint of reactivity, it is preferably 3 mmol/g or less, more preferably 2.5 mmol/g or less, and even more preferably 2 mmol/g or less.

Furthermore, from the viewpoint of obtaining a film with improved ice and snow resistance, the introduction rate of modifying groups in hydrophobic modified cellulose fibers is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more. From the viewpoint of reactivity, it is preferably 99 mol% or less, more preferably 97 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less.

[Method for producing modified cellulose fibers]
Among the modified cellulose fibers of component (A), the "anionic modified cellulose fiber having a type I crystal structure" of component (a) can be produced, for example, by a method that includes the step of introducing anionic groups into raw cellulose fibers to obtain anionic modified cellulose fibers.

Furthermore, the "hydrophobic modified cellulose fiber obtained by bonding a modifying group to one or more groups selected from the group consisting of anionic groups and hydroxyl groups of anionic modified cellulose fiber having a type I crystalline structure" of component (b) can be described, for example, by a method including (2) a step of bonding a modifying compound to anionic modified cellulose fiber obtained by a method including the step of (1) above to obtain hydrophobic modified cellulose fiber.

One embodiment of the process described in (2) above is:
Ingredient (A-1) Anionic modified cellulose fiber,
The process involves mixing one or more compounds selected from the group consisting of component (A-2) amino-modified silicone and hydrocarbon compounds having cationic groups, component (B) water, and component (C) an organic compound in liquid form at 25°C and 1 atm. This embodiment is the same as the process in the method for producing the emulsified composition of the present invention described later, namely the process of mixing components (A-1), (A-2), (B), and (C). According to this embodiment, hydrophobic modified cellulose fibers and the emulsified composition of the present invention can be produced in the same process, and therefore this can be said to be a more preferable production method.

(1) Step to obtain anionic modified cellulose fibers The anionic modified cellulose fibers used in the present invention can be obtained by subjecting raw material cellulose fibers to an oxidation treatment or an anionic group addition treatment to introduce at least one anionic group and thus anionic modification.

The cellulose fibers to be anionically modified, i.e., the cellulose fibers used as raw materials for hydrophobically modified cellulose fibers and anionically modified cellulose fibers, are preferably natural cellulose fibers from an environmental perspective. Examples include wood pulp such as coniferous pulp and hardwood pulp; cotton pulp such as cotton linters and cotton lint; non-wood pulp such as straw pulp and bagasse pulp; and bacterial cellulose. These can be used individually or in combination of two or more.

The average fiber diameter of the cellulose fibers used as raw material is not particularly limited, but from the viewpoint of handling ease and cost, it is preferably 1 μm or more, and preferably 300 μm or less.

Furthermore, while the average fiber length of the raw material cellulose fibers is not particularly limited, from the viewpoint of availability and cost, it is preferably 100 μm or more, and preferably 5,000 μm or less. The average fiber diameter and average fiber length of the raw material cellulose fibers can be measured according to the method described in the examples below. From the viewpoint of dispersibility, it is preferable to use cellulose fibers from the raw material that have been shortened by alkaline hydrolysis, acid hydrolysis, or the like, with an average fiber length of 1 μm or more and 1,000 μm or less.

Examples of anionic groups that can be introduced include carboxyl groups, sulfonic acid groups, or phosphate groups.

(i) When introducing a carboxyl group as an anionic group into cellulose fibers, for example, a method of oxidizing the hydroxyl group of cellulose to convert it into a carboxyl group, or a method of reacting the hydroxyl group of cellulose with at least one selected from the group consisting of a compound having a carboxyl group, an acid anhydride of a compound having a carboxyl group, and derivatives thereof.

The method for oxidizing the hydroxyl groups of the cellulose is not particularly limited, but for example, a method using 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst to react with an oxidizing agent such as sodium hypochlorite and a bromide such as sodium bromide can be applied. More specifically, known methods, such as the method described in Japanese Patent Application Publication No. 2011-140632, can be referenced.

By oxidizing cellulose fibers using TEMPO as a catalyst, the hydroxymethyl group ( _-CH2OH ) at the C6 position of the cellulose constituent unit is selectively converted to a carboxyl group. This method is particularly advantageous because it exhibits excellent selectivity for the hydroxyl group at the C6 position on the surface of the raw material cellulose fibers, and the reaction conditions are mild. Therefore, a preferred embodiment of the anionically modified cellulose fiber in the present invention is a cellulose fiber in which the C6 position of the cellulose constituent unit is a carboxyl group. In this specification, such cellulose fibers may be referred to as "oxidized cellulose fibers." Oxidized cellulose fibers are preferred because they are easier to prepare than other anionically modified cellulose fibers. Therefore, one preferred embodiment of the hydrophobically modified cellulose fiber in the present invention is a hydrophobicly modified cellulose fiber obtained by bonding an amino-modified silicone to a carboxyl group-containing cellulose fiber.

By further oxidation or reduction treatment of oxidized cellulose fibers, oxidized cellulose fibers from which residual aldehyde groups have been removed can be prepared.

(ii) When introducing a sulfonic acid group or a phosphate group as an anionic group into cellulose fibers, a method for introducing a sulfonic acid group as an anionic group into cellulose fibers is to add sulfuric acid to the cellulose fibers and heat them.
Methods for introducing phosphate groups as anionic groups into cellulose fibers include mixing cellulose fibers in a dry or wet state with powder or aqueous solution of phosphate or a phosphate derivative, or adding an aqueous solution of phosphate or a phosphate derivative to a dispersion of cellulose fibers. When these methods are employed, generally, after mixing or adding powder or aqueous solution of phosphate or a phosphate derivative, dehydration and heat treatment are performed.

(iii) Anionic modified cellulose fibers (component (A-1))
Anionic groups contained in the anionically modified cellulose fibers obtained in this way include, for example, carboxyl groups, sulfonic acid groups, and phosphate groups. From the viewpoint of the efficiency of introducing modifying groups into cellulose fibers, the anionic group is preferably a carboxyl group. Examples of ions that pair with the anionic groups (counterions) in the anionically modified cellulose fibers include metal ions such as sodium ions, potassium ions, calcium ions, and aluminum ions that are generated in the presence of alkali during production, and protons that are generated by substituting these metal ions with acid.

The anionic group content in anionically modified cellulose fibers is preferably 0.1 mmol/g or more, more preferably 0.4 mmol/g or more, even more preferably 0.6 mmol/g or more, and even more preferably 0.8 mmol/g or more, from the viewpoint of introducing modifying groups. Furthermore, from the viewpoint of improving handling properties, it is preferably 3 mmol/g or less, more preferably 2 mmol/g or less, and even more preferably 1.8 mmol/g or less. Note that "anionic group content" refers to the total amount of anionic groups in the cellulose constituting the cellulose fiber, and is specifically measured by the method described in the examples below.

From the viewpoint of handling ease, the average fiber diameter of the anion-modified cellulose fibers is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more. From the viewpoint of film strength, it is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. The average fiber diameter of the anion-modified cellulose fibers is measured by the method described in the examples below.

(2) Step to obtain hydrophobic modified cellulose fibers The hydrophobic modified cellulose fibers of component (b) can be produced by bonding one or more compounds selected from the group consisting of polymer compounds and hydrocarbon compounds having cationic groups to the anionic modified cellulose fibers. As such a production method, a known method, for example, the method described in Japanese Patent Application Publication No. 2015-143336, can be used.

(i) Polymer compounds The polymer compounds used as modifying compounds in the present invention can be commercially available or prepared according to known methods. Only one polymer compound may be used, or two or more polymer compounds may be used.

In this invention, the polymer compound used as the modifying compound is preferably a polymer compound having a repeating structure linked by an oxygen atom, more preferably a polymer compound having a repeating structure linked by an oxygen atom, such as a polyoxyalkylene structure or a polysiloxane structure, and even more preferably a silicone compound. Examples of silicone compounds include amino-modified silicones, epoxy-modified silicones, carboxy-modified silicones, carbinol-modified silicones, and hydrogen-modified silicones, and the position of the reactive group may be either on the side chain or at the end of the silicone compound. Among these, amino-modified silicones are preferred from the viewpoint of ease of modification.

(ii) Amino-modified silicones Amino-modified silicones are silicone compounds having amino groups. Preferably, the amino-modified silicone has a kinematic viscosity at 25°C of 10 ^mm² /s or more and 20,000 ^mm² /s or less. Furthermore, amino-modified silicones with an amino equivalent of 400 g/mol or more and 16,000 g/mol or less are preferred.

The kinematic viscosity at 25°C can be determined using an Ostwald viscometer. From the viewpoint of anti-icing and anti-snow properties, it is more preferably 20 ^mm² /s or more, and even more preferably 50 ^mm² /s or more. From the viewpoint of handling properties, it is more preferably 10,000 ^mm² /s or less, and even more preferably 5,000 ^mm² /s or less.

Furthermore, the amino equivalent is preferably 400 g/mol or more, more preferably 600 g/mol or more, and even more preferably 800 g/mol or more, from the viewpoint of ice and snow resistance, and preferably 16,000 g/mol or less, more preferably 14,000 g/mol or less, and even more preferably 12,000 g/mol or less, from the viewpoint of ease of bonding to anion-modified cellulose fibers. The amino equivalent is the molecular weight per nitrogen atom, and is calculated as: Amino equivalent (g/mol) = Mass-average molecular weight / Number of nitrogen atoms per molecule. Here, the mass-average molecular weight is the value obtained using gel permeation chromatography with polystyrene as the standard substance, and the number of nitrogen atoms can be determined by elemental analysis.

A specific example of an amino-modified silicone is the compound represented by general formula (a1).

[In the formula, ^R1a represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and is preferably a methyl group or a hydroxyl group from the viewpoint of anti-icing and anti-snow properties. ^R2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, or a hydrogen atom, and is preferably a methyl group or a hydroxyl group from the same viewpoint. B represents a side chain having at least one amino group, and ^R3a represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. x and y each represent the average degree of polymerization, and are selected so that the kinematic viscosity and amino equivalent of the compound at 25°C are within the above range. Note that ^R1a , ^R2a , and ^R3a may be the same or different, and multiple ^R2a may be the same or different.]

In the compound of general formula (a1), from the viewpoint of anti-ice and anti-snow properties, x is preferably a number between 10 and 10,000, more preferably between 20 and 5,000, and even more preferably between 30 and 3,000. y is preferably a number between 1 and 1,000, more preferably between 1 and 500, and even more preferably between 1 and 200. The mass-average molecular weight of the compound of general formula (a1) is preferably between 2,000 and 1,000,000, more preferably between 5,000 and 100,000, and even more preferably between 8,000 and 50,000.

In general formula (a1), the following can be considered as side chain B having an amino group.
-C ₃ H ₆ -NH ₂
-C ₃ H ₆ -NH-C ₂ H ₄ -NH ₂
-C ₃ H ₆ -NH- [C ₂ H ₄ -NH] _e -C ₂ H ₄ -NH ₂
-C ₃ H ₆ -NH(CH ₃ )
-C ₃ H ₆ -NH-C ₂ H ₄ -NH(CH ₃ )
-C ₃ H ₆ -NH-[C ₂ H ₄ -NH] _f -C ₂ H ₄ -NH(CH ₃ )
-C ₃ H ₆ -N(CH ₃ ) ₂
-C ₃ H ₆ -N(CH ₃ )-C ₂ H ₄ -N(CH ₃ ) ₂
-C ₃ H ₆ -N(CH ₃ )-[C ₂ H ₄ -N(CH ₃ )] _g -C ₂ H ₄ -N(CH ₃ ) ₂
-C ₃ H ₆ -NH-cyclo-C ₅ H ₁₁
(Here, e, f, and g are numbers from 1 to 30.)

The amino-modified silicone used in the present invention can be produced, for example, by hydrolyzing an organoalkoxysilane represented by general formula (a2) with excess water to obtain a hydrolysate, and then heating the hydrolysate obtained from this hydrolysate with dimethylcyclopolysiloxane using a basic catalyst such as sodium hydroxide to 80 to 110°C to allow an equilibrium reaction to occur, and then neutralizing the basic catalyst with an acid when the reaction mixture reaches a desired viscosity (see Japanese Patent Publication No. 53-98499).
_H2N ( _CH2 ) _2NH ( _CH2 ) _3Si ( _CH3 )( _OCH3 ) ₂ (a2)

Furthermore, as the amino-modified silicone, from the viewpoint of obtaining a film with high anti-freezing and anti-snow properties, it is preferably one or more selected from the group consisting of monoamino-modified silicone having one amino group in one of the side chains B and diamino-modified silicone having two amino groups in one of the side chains B, and more preferably one or more selected from the group consisting of a compound in which the amino-group-containing side chain _B is represented as _{-C3H6 - NH2} [hereinafter referred to as component (a1-1)] and a compound in which the amino-group-containing side chain B is represented as _-C3H6 -NH- _{C2H4 - NH2} [hereinafter referred to as component (a1-2)].

In this invention, the amino-modified silicones are, in terms of performance, TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600) and TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800) from Momentive Performance Materials, and SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700), SF8457C (kinematic viscosity: 1200, amino equivalent: 1800), SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), SF8452C (kinematic viscosity: 600, amino equivalent: 6400), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), and BY16-892 (kinematic viscosity: 1500, amino equivalent: 2800) from Dow Toray Industries, Inc. Preferred are KF-8002 (kinematic viscosity: 1100, amino equivalent: 1700), KF-8004 (kinematic viscosity: 800, amino equivalent: 1500), KF-8005 (kinematic viscosity: 1200, amino equivalent: 11000), KF-867 (kinematic viscosity: 1300, amino equivalent: 1700), KF-864 (kinematic viscosity: 1700, amino equivalent: 3800), and KF-859 (kinematic viscosity: 60, amino equivalent: 6000), all manufactured by Shin-Etsu Chemical Co., Ltd. In parentheses, the kinematic viscosity is measured at 25°C (unit: ^mm² /s), and the unit of amino equivalent is g/mol.

(a1-1) BY16-213 (kinematic viscosity: 55, amino equivalent: 2700) and BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are more preferred as component (a1-1).

(a1-2) Component (a1-2) is more preferably SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600), SF8452C (kinematic viscosity: 600, amino equivalent: 6400), KF-8002 (kinematic viscosity: 1100, amino equivalent: 1700), or SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700).

Furthermore, silicone compounds may have substituents. Examples of substituents include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, and hexyloxy groups; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, and sec-butoxycarbonyl groups. Examples include alkoxy-carbonyl groups with 1 to 6 carbon atoms, such as carbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, and isopentyloxycarbonyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine; acyl groups with 1 to 6 carbon atoms, such as acetyl and propionyl groups; aralkyl groups; aralkyloxy groups; alkylamino groups with 1 to 6 carbon atoms; and dialkylamino groups with 1 to 6 carbon atoms in the alkyl group.

(iii) Hydrocarbon compounds having cationic groups In the present invention, a hydrocarbon compound having cationic groups is a compound in which one or more hydrocarbon groups are bonded to one cationic group. The total number of carbon atoms in the hydrocarbon compound having cationic groups is preferably 16 or more, more preferably 18 or more, from the viewpoint of obtaining a film with high anti-ice and anti-snow properties, and preferably 40 or less, more preferably 30 or less, and even more preferably 26 or less, from the viewpoint of handling properties.

Hydrocarbon compounds having a cationic group are compounds in which the hydrocarbon group is directly bonded to a nitrogen atom or phosphorus atom via a covalent bond when the cationic group is a primary amine, secondary amine, tertiary amine, quaternary ammonium, phosphonium, etc. When the cationic group is an amidine, guanidine, etc., it is a compound in which the hydrocarbon group is covalently bonded to at least one of the nitrogen atoms or carbon atoms of the functional group. When the cationic group is an imidazolium, pyridinium, imidazoline, etc., it is a compound in which at least one hydrocarbon group is covalently bonded to any position in the ring structure.
Hydrocarbon compounds having cationic groups are more preferably those that do not contain oxyalkylene groups.

(vi) Hydrocarbon Groups Examples of hydrocarbon groups in the hydrocarbon compounds include chain saturated hydrocarbon groups, chain unsaturated hydrocarbon groups, cyclic saturated hydrocarbon groups, and aromatic hydrocarbon groups. From the viewpoint of availability, the number of carbon atoms in the hydrocarbon group is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, and from the same viewpoint, preferably 40 or less, more preferably 30 or less, and even more preferably 24 or less. Unless otherwise specified, the number of carbon atoms in a hydrocarbon group refers to the number of carbon atoms in a single hydrocarbon group.

Specific examples of chain-type saturated hydrocarbon groups include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, tert-pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, octadecyl group, docosyl group, octacosanyl group, and the like.

Specific examples of chain-type unsaturated hydrocarbon groups include, for example, ethenyl, propenyl, butenyl, isobutenyl, isoprenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, tridecenyl, tetradecenyl, and octadecenyl groups.

Specific examples of cyclic saturated hydrocarbon groups include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, cyclotridecyl group, cyclotetradecyl group, and cyclooctadecyl group.

The aromatic hydrocarbon group is selected from the group consisting of, for example, aryl groups and aralkyl groups. The aryl and aralkyl groups may be either substituted or unsubstituted aromatic rings.

Examples of aryl groups include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, triphenyl, terphenyl groups, and groups in which these groups are substituted with substituents described later.

Examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, phenylpentyl, phenylhexyl, phenylheptyl, and phenyloctyl groups, as well as groups in which the aromatic groups of these groups are further substituted with substituents.

The above hydrocarbon compounds may have some hydrogen atoms further substituted. Examples of substituents include fluorine, chlorine, bromine, iodine, hydroxyl, methoxy, ethoxy, carboxyl, aldehyde, ketone, and thiol groups.

The hydrocarbon compounds having the cationic group described above are preferably hydrocarbon compounds having an amino group, such as primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds (referred to as "hydrocarbon amines" in this specification). Specific examples of such hydrocarbon amines include hexadecylamine, stearylamine, oleylamine, dioctylamine, didecylamine, didodecylamine, trihexylamine, trioctylamine, tetrabutylammonium salt, tetrahexylammonium salt, dimethyldioctylammonium salt, dimethyldidecylammonium salt, and trimethylhexadecylammonium salt.

(v) Amount of modifying compound used In the process of obtaining hydrophobic modified cellulose fibers, the equivalent amount of functional groups of the modifying compound used that can react with the anionic groups in the anionic modified cellulose fibers is preferably 0.1 equivalents or more, more preferably 0.5 equivalents or more, and even more preferably 1 equivalent or more, from the viewpoint of ice prevention, snow prevention and durability, and from the same viewpoint, preferably 20 equivalents or less, more preferably 10 equivalents or less, and even more preferably 2 equivalents or less.

(3) Micronization process By micronizing the cellulose at any stage of the method for producing modified cellulose fibers, cellulose on a micrometer scale can be micronized to a nanometer scale. Since reducing the average fiber diameter to nanometer size improves the strength during film formation, it is preferable to further carry out the micronization process.

For the micronization process, known dispersers are preferably used. For example, disintegrators, beaters, low-pressure homogenizers, high-pressure homogenizers, grinders, cutter mills, ball mills, jet mills, short-screw extruders, twin-screw extruders, ultrasonic stirrers, and household juicer mixers can be used. Furthermore, the solid content of the reactant fibers in the micronization process is preferably 50% by mass or less.

<Component (B)>
In this invention, component (B) is water. Component (B) serves as a solvent in the production of modified cellulose fibers and as one of the constituent components of the emulsified composition of this invention.

<Component (C)>
In this invention, component (C) is a liquid organic compound at 25°C and 1 atm. Component (C) may also be a solvent used in the production of hydrophobic modified cellulose fibers.
At 25°C and 1 atm, the solubility of a liquid organic compound in water is preferably 10 g or less per 100 g of water at 25°C, and more preferably 1 g or less.
From the viewpoint of obtaining a film with improved ice-proof and snow-proof properties, the molecular weight of component (C) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less, and from the same viewpoint, preferably 100 or more, and more preferably 200 or more.

Component (C) in the present invention specifically includes oils, organic solvents, polymerizable monomers, prepolymers, etc. Component (C) in the present invention is preferably an oil. From the viewpoint of obtaining a film with improved anti-icing and anti-snow properties, the oil may be one or more selected from the group consisting of alcohols, ester oils, hydrocarbon oils, silicone oils other than modifying compounds, ether oils, fats and oils, fluorinated inert liquids, and fatty acids. Preferably, one or more selected from the group consisting of ester oils, silicone oils other than modifying compounds, ether oils, fats and oils, and fluorinated inert liquids are preferred. More preferably, one or more selected from the group consisting of silicone oils other than modifying compounds, SL oils, and ether oils are preferred, and silicone oil and/or SL oil are even more preferred.

Examples of ester oils include monoester oils, diester oils, and triester oils. Specific examples include aliphatic or aromatic monocarboxylic or dicarboxylic acid esters with 2 to 18 carbon atoms, such as isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, isopropyl palmitate, glyceryl tri-2-ethylhexanoate, and glyceryl triisostearate.

Examples of silicone oils other than modifying compounds include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.
Examples of oils and fats include vegetable oils such as soybean oil, coconut oil, linseed oil, cottonseed oil, rapeseed oil, and castor oil, as well as animal oils.

From the viewpoint of obtaining a film with improved anti-freezing and anti-snow properties, the compound of component (C) preferably has an SP value of 10 or less, more preferably 9.5 or less, even more preferably 9.0 or less, and even more preferably 8.5 or less. From the same viewpoint, it is preferably 6.0 or more, more preferably 6.5 or more.

In this specification, the SP value refers to the solubility parameter (unit: (cal/ ^cm³ ) ^¹/² ) calculated by the Fedors method, and is described, for example, in the references "Basic Principles, Applications, and Calculation Methods of SP Values" (Information Organization Co., Ltd., 2005) and Polymer Handbook Third Edition (A Wiley-Interscience publication, 1989).

Examples of oils with an SP value of 10 or less used in this invention include oleic acid (SP value: 9.2), D-limonene (SP value: 9.4), PEG400 (SP value: 9.4), dimethyl succinate (SP value: 9.9), neopentyl glycol dicaprate (SP value: 8.9), hexyl laurate (SP value: 8.6), isopropyl laurate (SP value: 8.5), isopropyl myristate (SP value: 8.5), isopropyl palmitate (SP value: 8.5), isopropyl oleate (SP value: 8.6), hexadecane (SP value: 8.0), olive oil (SP value: 9.3), jojoba oil (SP value: 8.6), squalane (SP value: 7.9), liquid paraffin (SP value: 7.9), and fluorine. Inert liquids (e.g., Fluorinert FC-40 (manufactured by 3M, SP value: 6.1), Fluorinert FC-43 (manufactured by 3M, SP value: 6.1), Fluorinert FC-72 (manufactured by 3M, SP value: 6.1), Fluorinert FC-770 (manufactured by 3M, SP value: 6.1)), silicone oils (e.g., KF96-1cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7) 3) Examples include KF-96-10cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-50cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-1000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96H-10,000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), etc.

<Component (D)>
The emulsified composition of the present invention may contain polyether-modified silicone compounds other than the modifying compound for component (D). By incorporating such component (D) into the emulsified composition, a film with improved anti-ice and anti-snow properties can be obtained. An example of component (D) is a compound having a methyl silicone chain as the main chain and side chains consisting of polyoxyethylene groups, and specifically, a compound represented by the following general formula can be mentioned.

(In the formula, ^R1 is a methylene group, an ethylene group, or a trimethylene group; ^R2 is an alkyl group having 1 to 4 carbon atoms; m is an integer from 0 to 50; n is an integer from 1 to 10; p is an integer from 1 to 50; and q is an integer from 0 to 50. - In the group represented ^{by R1} ( _C2H4O ) _p ( _C3H6O ) _q , ( _{C2H4O ) p and} ( _{C3H6O ) q} may be random or _blocky .)

The HLB value of the polyether-modified silicone compound is preferably within a specific range from the viewpoint of the durability of the film obtained by drying the emulsified composition. Specifically, it is preferably 1 or higher, more preferably 5 or higher, even more preferably 10 or higher, preferably 18 or lower, and more preferably 16 or lower.

When using two or more polyether-modified silicones with different HLB values, the weighted average of these values should fall within the above range. The HLB value is an index representing the balance between hydrophilicity and lipophilicity, and in this invention, it refers to the value obtained by the following Griffin formula.
HLB value = 20 × sum of molecular weights of hydrophilic bases / molecular weight

The kinematic viscosity of the polyether-modified silicone compound at 25°C is preferably within a specific range from the viewpoint of the durability of the film obtained by drying the emulsion composition. Specifically, it is preferably 1 ^mm² /s or more, more preferably 5 ^mm² /s or more, preferably 1000 ^mm² /s or less, more preferably 500 ^mm² /s or less, and even more preferably 200 ^mm² /s or less.

Polyether-modified silicone compounds that can be preferably used as component (D) are commercially available. Examples of commercially available products include "KF-615A", "KF-640", "KF-642", "KF-643", "KF-644", "KF-351A", "KF-354L", "KF-355A", "KF-6011", "KF-6012", "KF-6015", "KF-6016", "KF-6017", "KF-6020", and "KF-6043" (all are trade names), manufactured by Shin-Etsu Chemical Co., Ltd. From the viewpoint of the durability of the film obtained by drying the emulsion composition, "KF-640", "KF-642", "KF-643", "KF-351A", "KF-354L", and "KF-355A" can be preferably used. Commercially available products with structures that do not conform to the above general formula (for example, "KF-6028" and "KF-6038" manufactured by Shin-Etsu Chemical Co., Ltd. (both are product names)) can also be used as component (D).

<Component (E): Polymer compounds other than components (A) and (D)>
The emulsifying composition of the present invention may further contain a polymer compound other than components (A) and (D) (component (E)).
From the viewpoint of obtaining a film with high anti-ice and anti-snow properties, it is preferable that the polymer compound be one or more selected from the group consisting of polymer compound (X) and polymer compound (Y) described below.
Polymeric compound (X): A polymeric compound having an ester group, amide group, urethane group, amino group, ether group, or carbonate group in its main chain (however, polymeric compounds that fall under either component (A) or component (D) are not treated as polymeric compound (X)).
Polymer compound (Y): Methacrylic or acrylic polymer having ester or amide groups in its side chains.

From the viewpoint of obtaining a film with high anti-ice and anti-snow properties, the mass-average molecular weight of the polymer compound is preferably 1,000 or more, and from the same viewpoint, preferably 500,000 or less.

[High molecular compound (X)]
Examples of polymer compounds (X) having an ester group in the main chain include condensates of dicarboxylic acids such as adipic acid, sebacic acid, dodecanediic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenyl succinic acid with diols such as ethylene glycol, propylene glycol, and butanediol, or condensates of compounds such as glycolic acid and lactic acid that have both a hydroxyl group and a carboxyl group in one molecule.

Examples of polymer compounds (X) having an amide group in the main chain include condensates of dicarboxylic acids such as adipic acid, sebacic acid, dodecanediic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenyl succinic acid, and diamines such as aliphatic diamines such as ethylenediamine, hexamethylenediamine, and propylenediamine.

Examples of polymer compounds (X) having urethane groups in the main chain include polymers of diisocyanates such as triresin diisocyanate, diphenyl isocyanate, xylylene diisocyanate, and hexamethylene diisocyanate, and diols such as ethylene glycol, propylene glycol, and butanediol.

Examples of polymer compounds (X) having amino groups in the main chain include polymers of alkylimines such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, and hexyleneimine.

Examples of polymer compounds (X) having ether groups in the main chain include polymers of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and polymers of formaldehyde.

Examples of polymer compounds (X) having carbonate groups in the main chain include condensates of polyols such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, and 1,1-bis(4-hydroxyphenyl)cyclohexane with phosgene.

[High molecular compound (Y)]
Examples of methacrylic or acrylic polymers having ester or amide groups in their side chains (hereinafter also simply referred to as (meth)acrylic polymers) include polyalkyl (meth)acrylates such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, and polybutyl (meth)acrylate; copolymers with acrylics such as styrene acrylic and urethane acrylic; and poly(meth)acrylamides such as poly(meth)acrylamide, polyN-methyl (meth)acrylamide, polyN,N-dimethyl (meth)acrylamide, and polyN-phenyl (meth)acrylamide.
In the present invention, from the viewpoint of obtaining a film with high anti-ice and anti-snow properties, it is preferable that component (E) is a polymer compound containing a (meth)acrylic polymer.

<Other ingredients>
In addition to the components mentioned above, the emulsifying composition of the present invention may contain plasticizers, nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, hydrocarbon waxes and anionic surfactants as lubricants, ultraviolet absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, antifungal agents, antibacterial agents, foaming agents, surfactants; starches, polysaccharides such as alginic acid; natural proteins such as gelatin, glue, and casein; inorganic compounds such as tannins, zeolites, ceramics, and metal powders; fragrances; flow regulators; leveling agents; conductive agents; ultraviolet dispersants; deodorants, etc., to the extent that they do not impair the effects of the present invention. Similarly, other polymer materials and other compositions may be added to the extent that they do not hinder the effects of the present invention.

<Properties of Emulsified Compositions for Ice and Snow Prevention>
The emulsified composition for de-icing and snow protection of the present invention is an emulsified composition containing the above-mentioned components (A), (B), and (C) as essential components. Emulsification in the present invention is performed by applying mechanical force to a mixture of water and a liquid organic compound at 25°C and 1 atm, so that droplets of the other liquid are finely dispersed in one liquid. Either an o/w type emulsion or a w/o type emulsion may be used, but an o/w type emulsion is preferred.

From the viewpoint of emulsifying power, the content of component (A) in the emulsified composition or during mixing is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more. On the other hand, from the viewpoint of handling properties, it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

The content of component (B) in the emulsified composition or during mixing is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of maintaining the emulsified state, and preferably 98% by mass or less, from the viewpoint of effective content.

The content of component (C) in the emulsified composition or during mixing is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of maintaining the emulsified state. On the other hand, from the viewpoint of solution viscosity and handling properties, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

The mass ratio (A/C) of component (A) to component (C) in the emulsified composition or during mixing is preferably 0.0001 or higher, more preferably 0.001 or higher, even more preferably 0.004 or higher, even more preferably 0.01 or higher, and even more preferably 0.04 or higher, from the viewpoint of obtaining a film with improved anti-freezing and anti-snow properties. From the viewpoint of film formation, it is preferably 20 or lower, more preferably 10 or lower, even more preferably 5 or lower, even more preferably 3 or lower, and even more preferably 2 or lower. From these viewpoints, it is preferably 0.0001 to 20 or lower, more preferably 0.001 to 10 or lower, even more preferably 0.004 to 5 or lower, even more preferably 0.01 to 3 or even more preferably 0.04 to 2 or lower.

When the emulsified composition of the present invention contains component (D), the content of component (D) in the emulsified composition or during mixing is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of film durability. On the other hand, from the viewpoint of suppressing an increase in composition viscosity, it is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

When the emulsified composition of the present invention contains component (E), the content of component (E) in the emulsified composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of film durability, while preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of suppressing an increase in the viscosity of the composition.

The viscosity of the emulsified composition is not particularly limited, but from a handling standpoint, the viscosity at 25°C is preferably 0.5 mPa·s or higher, more preferably 0.8 mPa·s or higher, and even more preferably 1 mPa·s or higher. Similarly, from the same viewpoint, it is preferably 30 Pa·s or lower, more preferably 20 Pa·s or lower, and even more preferably 10 Pa·s or lower. Here, viscosity was measured using a B-type viscometer with an appropriate rotor matched to the viscosity range of each sample, after stirring for 1 minute at 25°C and a rotation speed of 60 rpm.

From the viewpoint of improving ice and snow resistance and their durability, the average particle size of the emulsion droplets in the emulsion composition is preferably 10 nm or larger, more preferably 50 nm or larger, and even more preferably 100 nm or larger, as measured by SEM observation described later. Similarly, from the same viewpoint, it is preferably 2000 nm or smaller, more preferably 1000 nm or smaller, even more preferably 700 nm or smaller, even more preferably 500 nm or smaller, preferably 10 nm to 2000 nm, more preferably 50 nm to 1000 nm, and even more preferably 100 nm to 500 nm.

2. Method for Producing an Emulsified Composition for Ice and Snow Protection The method for producing the emulsified composition for ice and snow protection of the present invention comprises a step of mixing the aforementioned components (A), (B), (C), etc. Here, a liquid organic compound may be mixed with an aqueous dispersion of modified cellulose fibers at 25°C and 1 atm, or the organic compound dispersion of modified cellulose fibers may be mixed with water.

Alternatively, a method for producing the emulsified composition of the present invention includes a step of mixing component (A-1), component (A-2), component (B), and component (C). This method is more preferable because the step of obtaining hydrophobic modified cellulose fibers and the step of obtaining the emulsified composition can be achieved in a single step. There are no restrictions on the mixing order in this method. For example, component (A-1), component (A-2), and component (B) may be mixed first, followed by component (C), or component (A-1), component (A-2), and component (C) may be mixed first, followed by component (B).
Preferably, the manufacturing method includes a step of mixing component (A-1) and component (A-2) in the presence of component (B) and component (C).
Accordingly, a preferred embodiment of the emulsified composition of the present invention contains component (A-1), component (A-2), component (B), and component (C). In this case, the content of component (A) is the total content of component (A-1) and component (A-2).

When incorporating component (D) and/or component (E), component (D) and/or component (E) may be mixed together with component (A-1), component (A-2), component (B), and component (C), and component (D) and/or component (E) may be added to the emulsified composition obtained using these components.

By mixing the components, emulsification occurs, yielding an emulsified composition. For this mixing process, a magnetic stirrer, mechanical stirrer, homomixer, vacuum emulsifier, low-pressure homogenizer, high-pressure homogenizer, grinder, cutter mill, ball mill, jet mill, short-screw extruder, twin-screw extruder, ultrasonic stirrer, household juicer mixer, etc. The mixing process may also be carried out by combining two or more operations.

The temperature and time for mixing each component are not particularly limited; for example, a temperature range of 5 to 50°C is preferred, and a range of 1 minute to 3 hours is preferred.

The preferred range of content for each component during mixing is the same as the preferred range of content for each component in the emulsified composition of the present invention described above.

When using components (A-1) and (A-2) instead of component (A), it is preferable that the upper and lower limits of the preferred content of component (A) be set as the upper and lower limits of the total amount of both components. Here, regarding the mixing ratio of component (A-1) and component (A-2), from the viewpoint of anti-icing, anti-snowing properties and their durability, component (A-2) is preferably 0.1 equivalents or more, more preferably 0.3 equivalents or more, and even more preferably 0.5 equivalents or more relative to the anionic group of component (A-1). On the other hand, from the viewpoint of the stability of the emulsified composition, it is preferably 3 equivalents or less, more preferably 2 equivalents or less, and even more preferably 1.5 equivalents or less.

Alternatively, the ratio of the total number of moles of the amino groups of the amino-modified silicone and the total number of moles of the hydrocarbon compound with cationic groups (16 to 40 carbon atoms) in component (A-2) to the number of moles of the anionic groups of component (A-1) ([total number of moles of component (A-2)] / [number of moles of anionic groups of component (A-1)]) is preferably 0.1 or higher, more preferably 0.3 or higher, and even more preferably 0.5 or higher from the viewpoint of obtaining a film with improved ice-proofing, snow-proofing, and durability. From the viewpoint of film-forming properties, it is preferably 3 or lower, more preferably 2 or lower, and even more preferably 1.5 or lower. The number of moles of the anionic groups in the anionic-modified cellulose fiber can be obtained by multiplying the amount of anionic-modified cellulose fiber used (g) by the anionic group content (moles/g), and the number of moles of the amino groups in the amino-modified silicone can be obtained by dividing the amount of amino-modified silicone used (g) by the amino equivalent (g/mol).

Furthermore, the mass ratio (A-2/C) of component (A-2) to component (C) is preferably 0.0001 or higher, more preferably 0.001 or higher, even more preferably 0.004 or higher, even more preferably 0.01 or higher, and even more preferably 0.04 or higher, from the viewpoint of obtaining a film with improved ice-proofing, snow-proofing, and durability. From the viewpoint of film-forming properties, it is preferably 20 or lower, more preferably 10 or lower, even more preferably 5 or lower, even more preferably 3 or lower, and even more preferably 2 or lower. From these viewpoints, it is preferably 0.0001 to 20 or lower, more preferably 0.001 to 10 or lower, even more preferably 0.004 to 5 or lower, even more preferably 0.01 to 3 or even more preferably 0.04 to 2 or lower.

3. Method for producing anti-ice and anti-snow film The method for producing a film containing modified cellulose fibers according to the present invention includes the steps of applying and drying the emulsified composition of the present invention.

Specifically, the emulsified composition is applied to a substrate, such as a solid surface made of glass, resin, metal, ceramics, concrete, wood, stone, or fiber, or to skin, hair, etc. Application methods include, but are not limited to, application using an applicator, bar coater, spin coater, roller, etc., as well as brush application, hand application, air spray, airless spray, trigger spray, dip coating, etc.

From the viewpoint of film durability, the thickness of the emulsion composition coating on the substrate is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more. From the viewpoint of coatability, it is preferably 2000 μm or less, and more preferably 1500 μm or less.

Next, the emulsion composition coating film can be dried to obtain a coating film. The drying conditions can be under reduced pressure or atmospheric pressure, and the temperature range is preferably between 15°C and 75°C. Furthermore, the drying time is preferably between 1 hour and 24 hours.

4. Anti-Ice and Anti-Snow Films The anti-ice and anti-snow films obtained by the above manufacturing method preferably exhibit the synovial surface properties described in the literature (Technology of Superhydrophobic, Superoleophobic, and Synovial Surfaces / Publisher: Hiroshi Motoki / Distributor: Science & Technology Co., Ltd. / Published January 28, 2016). A smaller value for the sliding angle indicates higher synovial properties of the film.

The anti-ice and anti-snow film, by containing the aforementioned polyether-modified silicone compound, exhibits further improved durability.

The thickness of the film of the present invention is not particularly limited. From the viewpoint of film durability, it is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more. From the viewpoint of economic efficiency, it is preferably 2000 μm or less, more preferably 1200 μm or less, even more preferably 500 μm or less, and even more preferably 200 μm or less. The film thickness can be set to a desired value by adjusting the film thickness using an applicator or other coating tool, and by adjusting the ratio of the medium. The film thickness can be measured according to the method described in the examples below.

The film of the present invention is preferable because higher smoothness leads to higher synovial properties. Specifically, from the viewpoint of cost-effectiveness, the arithmetic mean roughness of the film immediately after manufacturing is preferably 0.3 μm or more, more preferably 0.5 μm or more, and even more preferably 0.8 μm or more. On the other hand, from the viewpoint of adhesion inhibition, it is preferably 40 μm or less, more preferably 35 μm or less, and even more preferably 30 μm or less. The arithmetic mean roughness of the film can be measured according to the method described in the examples below.

The film of the present invention is preferably highly durable. The durability of the film can be evaluated, for example, by the degree of increase in the arithmetic mean roughness of the film after contact with water for a certain period, or by the presence or absence of synovial properties. Specifically, if the arithmetic mean roughness of the film after 5 minutes of dropping is less than or equal to twice the roughness before dropping, and the film retains synovial properties after 5 minutes, then the film can be evaluated as highly durable.

The amount of modified cellulose fibers in the film of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more, from the viewpoint of film durability, and preferably 65% by mass or less, more preferably 36% by mass or less, and even more preferably 16% by mass or less, from the viewpoint of anti-ice and anti-snow properties. The amount of modified cellulose fibers in the film can be determined by considering the amount of volatile components (e.g., water and some oils) in the emulsified composition.
The preferred range of amounts of component (C) and/or component (E) in the film of the present invention also corresponds to the preferred range of amounts of those components in the emulsified composition.

The film of the present invention may contain optional components that do not impair the effects of the present invention. The content of these optional components in the film is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.5% by mass or more, preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

5. Structure The structure formed by drying the anti-icing and anti-snow emulsifying composition of the present invention and forming a coating film on the substrate can modify the surface of the substrate into a synovial surface. The film of the present invention can be suitably used as a covering material for roofs, building walls and fences, solar panels, road equipment such as signs and billboards and traffic lights, airplanes, automobiles, train vehicles and power lines, or clothing. As a result, it can be suitably used as an anti-icing and anti-snow film that suppresses the adhesion of snow and ice.

The emulsified composition of the present invention is useful as an anti-icing agent and snow-preventing agent. By applying the emulsified composition of the present invention to the above-mentioned substrate, it can be used as an anti-icing method or snow-preventing method.

The film in the present invention can be obtained by drying the emulsifying composition of the present invention, for example,
(A) One or more modified cellulose fibers selected from the group consisting of the following components (a) and (b),
(a) Anionic modified cellulose fibers having a type I crystal structure
(b) Hydrophobic modified cellulose fibers having a type I crystalline structure, wherein a modifying group is bonded to one or more groups selected from the group consisting of anionic groups and hydroxyl groups, and (c) an organic compound that is liquid at 25°C and 1 atm.
It is a film containing and having a particulate structure.

It is believed that the removal of water from the emulsified composition through drying causes the cellulose fibers that formed the emulsified particles to form a networked particulate structure. Furthermore, it is presumed that the improved durability is due to at least a portion of component (C) being contained within the particulate structure.

The maximum particle length, as observed by SEM, is preferably 10 to 2000 nm, more preferably 50 to 1000 nm, from the viewpoint of improving anti-ice and anti-snow properties and their durability. The maximum length refers to the longest length among the length, width, and height, assuming the particles are contained within the smallest possible rectangular parallelepiped. The preferred numerical ranges and embodiments of each component of the film are the same as those for the preferred numerical ranges and embodiments in the emulsified composition described above.

The present invention will be specifically described below with reference to examples. Note that the following examples are merely illustrative of the present invention and do not imply any limitation.

[Average fiber diameter, average fiber length, and average aspect ratio of anionically modified cellulose fibers and hydrophobically modified cellulose fibers]
Water is added to the cellulose fibers to be measured to prepare a dispersion with a water content of 0.0001% by mass. This dispersion is dropped onto mica and dried to create an observation sample. An atomic force microscope (AFM) (Digital Instruments, Nanoscope II Tappingmode AFM; probe used: Nanosensors, Point Probe (NCH)) is used to measure the fiber height (difference in height between areas with and without fibers) of the cellulose fibers in the observation sample. At that time, more than 100 cellulose fibers are extracted from the microscope image in which the cellulose fibers can be confirmed, and the average fiber diameter is calculated from their fiber heights. The average fiber length is calculated from the distance in the direction of the fibers. The average aspect ratio is calculated from the average fiber length / average fiber diameter. The height analyzed in the AFM image can be considered as the fiber diameter.

[Average fiber diameter and average fiber length of the cellulose fibers used as raw material]
A dispersion containing 0.01% by mass of deionized water is prepared by adding deionized water to the cellulose fibers to be measured. This dispersion is measured using a wet dispersion type image analysis particle size distribution analyzer (Jusco International Co., Ltd., product name: IF-3200) under the following conditions: front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 μm/pixel, syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold: 8, analysis sample volume: 1 mL, sampling: 15%. More than 100 cellulose fibers are measured, and their average ISO fiber diameter is used as the average fiber diameter, and their average ISO fiber length is used as the average fiber length.

[Anionic group content of anionic-modified cellulose fibers and hydrophobic-modified cellulose fibers]
Place 0.5 g of the cellulose fiber to be measured (dry weight) into a 100 mL beaker, add deionized water or a methanol/water = 1/2 mixture to make a total volume of 55 mL, and add 5 mL of 0.01 M sodium chloride aqueous solution to prepare a dispersion. Stir the dispersion until the cellulose fiber to be measured is sufficiently dispersed. Add 0.1 M hydrochloric acid to this dispersion to adjust the pH to 2.5-3, and using an automatic titrator (Toa DKK Co., Ltd., product name "AUT-701"), add 0.05 M sodium hydroxide aqueous solution dropwise to the dispersion with a waiting time of 60 seconds, and measure the conductivity and pH values every minute. Continue the measurement until the pH reaches approximately 11 to obtain a conductivity curve. From this conductivity curve, determine the amount of sodium hydroxide titration, and calculate the anionic group content of the cellulose fiber to be measured using the following formula.
Anionic group content (mol/g) = [Sodium hydroxide titration volume × Sodium hydroxide aqueous solution concentration (0.05 M)] / [Mass of cellulose fiber to be measured (0.5 g)]

[Aldehyde group content of oxidized cellulose fibers]
The carboxyl group content of the oxidized cellulose fiber to be measured is determined by the method for measuring the anionic group content described above.
Separately, 100 g of an aqueous dispersion of the oxidized cellulose fibers to be measured (solid content 1.0% by mass), 100 g of acetate buffer (pH 4.8), 0.33 g of 2-methyl-2-butene, and 0.45 g of sodium chlorite are added to a beaker and stirred at 25°C for 16 hours to oxidize the aldehyde groups remaining in the oxidized cellulose fibers. After the reaction is complete, the fibers are washed with deionized water to obtain cellulose fibers from which the aldehyde groups have been oxidized. The reaction solution is freeze-dried, and the carboxyl group content of the resulting dried product is measured using the method for measuring the anionic group content described above to calculate the "carboxyl group content of the oxidized cellulose fibers." Subsequently, the aldehyde group content of the oxidized cellulose fibers to be measured is calculated using Equation 1.

Aldehyde group content (molecules/g) = (Carboxy group content of oxidized cellulose fiber) - (Carboxy group content of oxidized cellulose fiber to be measured) ... Equation 1

[Solid content in the dispersion]
Measurements are taken using a halogen moisture meter (Shimadzu Corporation; product name "MOC-120H"). Measurements are taken every 30 seconds at a constant temperature of 150°C for 1 g of sample, and the value at which the mass loss is 0.1% or less of the initial amount of sample is defined as the solid content.

[Confirmation of crystalline structure in various types of cellulose fibers]
The various crystal structures of hydrophobic modified cellulose fibers and other materials are confirmed by measuring them using an X-ray diffractometer (MiniFlexII, Rigaku Corporation) under the following conditions.
The measurement conditions are as follows: X-ray source: Cu/Kα-radiation, tube voltage: 30 kV, tube current: 15 mA, measurement range: diffraction angle 2θ = 5 to 45°, X-ray scan speed: 10°/min. The sample for measurement is prepared by compressing it into a pellet with an area of 320 ^mm² and a thickness of 1 mm. The degree of crystallinity of the cellulose type I crystal structure is calculated from the obtained X-ray diffraction intensity based on the following formula A.

<Formula A>
Cellulose type I crystallinity (%) = [(I _22.6 - I _18.5 ) / I _22.6 ] × 100
[In the formula, I _22.6 represents the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, and I _18.5 represents the diffraction intensity of the amorphous region (diffraction angle 2θ = 18.5°)]

On the other hand, if the degree of crystallinity obtained by formula A above is 35% or less, from the viewpoint of improving calculation accuracy, it is preferable to calculate it based on the following formula B, in accordance with the description on pages 199-200 of the "Manual for Experiments in Wood Science" (edited by the Japan Wood Research Society; published in April 2000).
Therefore, if the degree of crystallinity obtained by formula A above is 35% or less, the value calculated based on the following formula B can be used as the degree of crystallinity.

<Formula B>
Cellulose type I crystallinity (%) = [ _Ac / ( _Ac + _Aa )] × 100
[In the formula, A _c is the sum of the peak areas of the lattice planes (002 plane) (diffraction angle 2θ = 22.6°), (011 plane) (diffraction angle 2θ = 15.1°), and (0-11 plane) (diffraction angle 2θ = 16.2°) in X-ray diffraction, A _a is the peak area of the amorphous region (diffraction angle 2θ = 18.5°), and each peak area is obtained by fitting the obtained X-ray diffraction chart with a Gaussian function.]

[Cellulose fiber (equivalent amount) in hydrophobic modified cellulose fibers]
The cellulose fiber (equivalent amount) in hydrophobic modified cellulose fibers is measured by the following method.
(1) When only one type of "modifying compound" is added, the amount of cellulose fiber (converted amount) is calculated using the following formula C.
<Formula C>
Cellulose fiber content (converted amount) (g) = Mass of hydrophobic modified cellulose fiber (g) / [1 + Molecular weight of modifying compound (g/mol) × Amount of modifying group bonded (mol/g) × 0.001]
(2) When there are two or more types of "modifying compounds" added, the amount of cellulose fiber (converted amount) is calculated by considering the molar ratio of each compound (i.e., the molar ratio when the total molar amount of added compounds is set to 1).

[Measurement of viscosity of emulsified compositions]
Using a Type B viscometer (Toki Sangyo TVB-10) with rotor No. 1, the viscosity was measured at 25°C, a rotation speed of 60 RPM, and after 1 minute.

[Observation of emulsified compositions using Cryo-SEM]
Observation of the emulsified composition using cryo-SEM is performed using a Scios DualBeam field emission scanning electron microscope manufactured by FEI. Observation is performed while gradually sublimating the water from the frozen emulsified composition. Observation is performed at an acceleration voltage of 2 kV and a magnification of 25,000x.

[Measuring the particle size of emulsified droplets using laser diffraction]
The particle size of emulsion droplets is measured using laser diffraction with a HORIBA LA-960 laser diffraction analyzer.
Measurement conditions: Water is added to the measurement cell, and the volume particle size distribution and volume median particle size (D ₅₀ ) are measured at a concentration that results in an appropriate absorbance range. The relative refractive index is 1.20, the temperature is 25°C, the circulation pump is ON, the circulation speed is 5, and the stirring speed is 5.

[Preparation of anionically modified cellulose fibers]
Preparation Example 1
Bleached coniferous kraft pulp (manufactured by Westfrey, trade name: Hinton) was used as the raw material for the natural cellulose fiber. A commercially available TEMPO (manufactured by Aldrich, Free Radical, 98% by mass) was used. Commercially available sodium hypochlorite, sodium bromide, and sodium hydroxide were also used.

First, 10 g of bleached kraft pulp fiber and 990 g of deionized water were weighed into a 2 L PP beaker equipped with a mechanical stirrer and stirring blades. The mixture was stirred at 25°C and 100 rpm for 30 minutes. Then, 0.13 g of TEMPO, 1.3 g of sodium bromide, and 35.5 g of 10.5% by mass sodium hypochlorite aqueous solution were added to 10 g of the pulp fiber in that order. Using an automatic titrator (Toa DKK Co., Ltd., product name: AUT-701), a pH stat titration was performed, and a 0.5 M sodium hydroxide aqueous solution was added dropwise to maintain the pH at 10.5. The reaction was carried out at 100 rpm at 25°C for 120 minutes. After that, the addition of the sodium hydroxide aqueous solution was stopped, and a suspension of anionically modified cellulose fiber was obtained.

The obtained suspension of anionically modified cellulose fibers was treated with 0.01 M hydrochloric acid to adjust the pH to 2. The filtrate was then thoroughly washed with deionized water using a compact electrical conductivity meter (Horiba LAQUAtwin EC-33B) until its conductivity was measured at 200 μs/cm or less. Following this, dehydration was performed to obtain anionically modified cellulose fibers. The carboxyl group content of these anionically modified cellulose fibers was 1.50 mmol/g, and the aldehyde group content was 0.23 mmol/g.

Preparation Example 2 (Production of finely processed anion-modified cellulose fibers)
In Preparation Example 1, 100 g of a suspension (solid content 2.0% by mass) was prepared by adding deionized water to the anionically modified cellulose fibers finally obtained. To this, a 0.5 M sodium hydroxide aqueous solution was added to adjust the pH to 8, and then deionized water was added to make a total of 200 g. This suspension was subjected to micronization treatment three times at 150 MPa using a high-pressure homogenizer (Yoshida Machinery Co., Ltd., product name: NanoVeta L-ES) to obtain a dispersion of micronized anionically modified cellulose fibers (solid content 1.0% by mass). The counterion of the carboxyl group in these micronized anionically modified cellulose fibers was a sodium ion. These micronized anionically modified cellulose fibers are abbreviated as "TCNF (Na type)".

Preparation Example 3 (Production of finely textured anionic modified cellulose fibers with reduced aldehyde groups)
182 g of the finely pulverized anionic modified cellulose fiber dispersion (solid content 1.0% by mass) obtained in Preparation Example 2 was weighed out, and deionized water was added to make a total of 400 g. 1.2 mL of 0.1 M sodium hydroxide aqueous solution and 120 mg of sodium borohydride were added, and the mixture was stirred at 25°C for 4 hours. Next, 9 mL of 1 M hydrochloric acid was added to carry out protonation. After the reaction was complete, the mixture was filtered, and the resulting cake was washed six times with deionized water to remove the salt and hydrochloric acid, obtaining a finely pulverized anionic modified cellulose fiber dispersion (solid content 0.9% by mass) in which the aldehyde groups had been reduced. The carboxyl group content of the obtained cellulose fibers was 1.50 mmol/g, and the aldehyde group content was 0.02 mmol/g. The carboxyl groups in these finely pulverized anionic modified cellulose fibers are in the free acid form (COOH), and are abbreviated as "TCNF (H type)". The crystallinity of these finely processed anion-modified cellulose fibers was 30%, the average fiber diameter was 3.3 nm, and the average fiber length was 600 nm.

[Preparation of hydrophobic modified cellulose fibers and emulsified compositions]
Example 1
In a beaker, 66.7 g (solid content 0.9 mass%) of the finely pulverized anion-modified cellulose fiber dispersion obtained in Preparation Example 3, 6.0 g of silicone oil 1, and 1.91 g of amino-modified silicone 1 as a modifying compound (corresponding to 1.25 equivalents relative to the carboxyl groups of the anion-modified cellulose fibers) were mixed, and deionized water was added to make a total of 100 g. This dispersion was stirred with a mechanical stirrer at room temperature for 5 minutes, and then subjected to 10 passes at 150 MPa using a high-pressure homogenizer (Yoshida Machinery Co., Ltd., product name: NanoVeta L-ES) to obtain an emulsion composition containing hydrophobic modified cellulose fibers in which amino-modified silicone was ionically bonded to the anion-modified cellulose fibers. The obtained composition was a cloudy liquid, and since oil droplets were observed to be dispersed in water using an optical microscope, it was determined to be an emulsion composition. The average emulsion particle size measured by laser diffraction was 300 nm.

Example 2
100 g of the emulsified composition obtained in Example 1 was weighed into a beaker, 0.2 g of polyether-modified silicone 1 was added thereto, and the mixture was stirred at 25°C for 30 minutes to obtain the emulsified composition.

Example 3
An emulsion composition containing hydrophobic modified cellulose fibers, in which amino-modified silicone is bonded to anionic-modified cellulose fibers via ionic bonds, was obtained in the same manner as in Example 1, except that the amount of silicone oil 1 was 2.0 g. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

Example 4
An emulsion composition containing hydrophobic modified cellulose fibers, in which amino-modified silicone is bonded to anionic-modified cellulose fibers via ionic bonds, was obtained in the same manner as in Example 1, except that silicone oil 2 was used instead of silicone oil 1. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

Example 5
An emulsion composition containing hydrophobic modified cellulose fibers, in which amino-modified silicone is bonded to anionic-modified cellulose fibers via ionic bonds, was obtained in the same manner as in Example 1, except that silicone oil 3 was used instead of silicone oil 1. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

Example 6
To the emulsified composition of Example 2, 3.3 g of styreneacrylic 1 emulsion (45% solids content) was added and stirred to obtain an emulsified composition.

Example 7
To the emulsion composition of Example 2, 6.6 g of styrene acrylic 1 emulsion (45% solids content) was added and stirred to obtain an emulsion composition.

Example 8
To the emulsion composition of Example 2, 13.2 g of styrene acrylic 1 emulsion (45% solids content) was added and stirred to obtain an emulsion composition.

Example 9
To the emulsion composition of Example 2, 20.3 g of urethane 1 emulsion (solid content 29.5%) was added and stirred to obtain an emulsion composition.

Example 10
An emulsion composition was prepared in the same manner as in Example 1, except that 0.30 g of oleylamine (corresponding to 1.25 equivalents relative to the carboxyl groups of the anionically modified cellulose fibers) was added instead of amino-modified silicone 1. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

Example 11
An emulsion composition was prepared in the same manner as in Example 1, except that isopropyl palmitate was used instead of silicone oil 1. To 100 g of the obtained emulsion composition, 0.2 g of polyether-modified silicone 1 was added and stirred to obtain an emulsion composition.

Comparative Example 1
As Comparative Example 1, a commercially available snow-repellent paint, "Kansai Paint's Rakuyuki Paint," was used as the coating liquid. This snow-repellent paint is a paint in which an acrylic synthetic resin and pigment are dispersed in an organic solvent, and therefore does not fall under the category of the emulsified composition of the present invention.

Comparative Example 2
As a comparative example 2, a surface with a textured structure coated with lubricating oil was prepared. Specifically, a water-repellent sheet with a textured structure (Toyal Ultra Lotus®, manufactured by Toyo Aluminum Co., Ltd.) was attached to a glass substrate (10 cm x 10 cm x 5 mm thick) with cellophane tape. 0.19 g of silicone oil ¹ as a lubricant was applied to 100 cm² of the water-repellent sheet to create a lubricating oil coated surface film with a thickness of 20 μm.

Details of the representative components used in the examples are summarized below.
[Modification compound]
Amino-modified silicone 1: DOWSIL ^™ SS-3551 manufactured by Dow Toray, kinematic viscosity: 1,000, amino equivalent: 1,700
Oleylamine: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
[Component (C)]
Silicone oil 1: Shin-Etsu Chemical Co., Ltd. "KF-96-100cs", SP value: 7.3
Silicone oil 2: Shin-Etsu Chemical Co., Ltd. "KF-96-10cs", SP value: 7.3
Silicone oil 3: Shin-Etsu Chemical Co., Ltd. "KF-96-3000cs", SP value: 7.3
Isopropyl palmitate: Manufactured by Fujifilm Wako Pure Chemical Industries, SP value: 8.5
[Component (D)]
Polyether-modified silicone 1: KF-640 manufactured by Shin-Etsu Chemical Co., Ltd., HLB: 14
[Component (E)]
Styrene-acrylic 1: Daicel Ornex Co., Ltd. "VIACRYL VSC 6286w/45WA"
Urethane 1: Daicel Ornex Co., Ltd., DAOTAN TW 6450/30WA, solids content 29.5%

[Preparation of a dried film]
The emulsified compositions prepared in Examples 1 to 11 and the coating liquid prepared in Comparative Example 1 were each applied to separate glass substrates (10 cm x 10 cm x 5 mm thick) and spread over the entire surface of the glass substrate. Then, the substrates were dried for 24 hours at 1 atmosphere, 25°C, and approximately 40% RH to form films. The thickness of each film was measured using the measurement method described below, and all were found to be 20 μm.
For Comparative Example 1, the coating solution was spread with a brush onto the same glass substrate as in the example, so that the film thickness after drying was 20 μm. The film was then dried for 24 hours at 1 atmosphere, 25°C, and approximately 40% RH.

[Measurement of film thickness]
The thickness of the film after drying was measured using a laser microscope (Keyence VK-9710) under the following conditions: objective lens: 10x, light intensity: 3%, brightness: 1548, Z pitch: 0.5 μm. A portion of the film was scraped off with a metal spatula to expose the glass substrate. The sample was then measured, and the height of the glass substrate and the height of the filmed portion were measured using the built-in image processing software. The film thickness was determined by taking the difference between these two values.

Test Example 1: <Ice-Sliding Performance Evaluation Test>
Each substrate with the above-described film formed on it, as well as the glass substrate itself, was fixed to a 45° inclined stand with double-sided tape (Scotch Super Multi-Purpose Double-Sided Tape, 12mm wide, manufactured by 3M). Next, in a room at 2°C, crushed ice was sprinkled onto the surface of each substrate using an electric ice shaver (DTY19, manufactured by Doshisha), and the amount of ice remaining on the substrate was measured. The specific criteria for evaluating the ice-sliding properties are as follows; a higher value indicates that the film has higher ice-sliding properties. The specific gravity of the crushed ice was 0.49 g/ ^cm³ .

5: More than 90% of the ice slid off.
4. More than 80% but less than 90% of the ice slid off.
3. More than 50% but less than 80% of the ice slid down.
2: More than 20% but less than 50% of the ice slid down.
1: Less than 20% of the ice slid off.

Test Example 2: <Snow-Sliding Performance Evaluation Test>
The snow-sliding properties were evaluated in a low-temperature test chamber (1°C) manufactured by MTS Snow and Ice Research Institute. A 1cm x 2cm x 2mm thick stainless steel piece was attached to the back of each substrate with the above-mentioned film formed on it, as well as the glass substrate itself, using double-sided tape (Scotch Super Multi-Purpose Double-Sided Tape, 12mm wide, manufactured by 3M). The substrates were then placed on a fixed stand equipped with a magnet so that they were at a 90° angle. Next, artificial snow was blown onto the front of the substrate at a wind speed of 5 m/s for 30 minutes, and the snow-sliding properties were evaluated according to the following criteria. A higher value indicates that the film has higher snow-sliding properties. The specific gravity of the artificial snow was 0.29 g/ ^cm³ .

Ski within 5:10 minutes.
Ski within 4:15 minutes.
Ski within 3 hours and 20 minutes.
Ski within 2 hours and 30 minutes.
1. I did not ski within the 30-minute test time.

Test Example 3 <Scratch Resistance Evaluation>
The film surface was observed using a laser microscope after the snow-skid performance evaluation test, and its scratch resistance was evaluated according to the following criteria. A higher numerical value indicates greater scratch resistance of the film. Note that the number of scratches on the film before the snow-skid performance evaluation test was less than 10% of the film area in the observation field.

4. The damaged area accounts for less than 10% of the film's surface area within the observation field, and the surface condition is almost the same as the initial state.
3. The damaged area covers 10% to less than 20% of the membrane area in the field of view.
2. The damaged area covers more than 20% but less than 50% of the membrane area in the field of view.
1. The damaged area covers more than 50% of the membrane area in the field of view.

Test Example 4 <Weather Resistance Evaluation>
Using a Super Xenon Weather Meter SX75 (manufactured by Suga Test Instruments), accelerated weathering tests were conducted on substrates on which the films produced in Example 2 and Comparative Example 2 were formed, under the conditions of irradiance: 180 W/ ^m² , BPT: 63°C, humidity: 50% RH, and 3000 hours.
As a result, the film prepared from the emulsified composition of Example 2 did not yellow even after 3000 hours and maintained high de-icing properties, indicating excellent weather resistance. On the other hand, the film of Comparative Example 2 yellowed severely after 3000 hours and disintegrated, indicating low weather resistance, i.e., low film durability.

The composition and evaluation results of each component are shown in Tables 1 and 2. The amounts of each component in Tables 1 and 2 are in mass percent. Note that due to rounding, the sum of the components may not equal 100% by mass.

Tables 1 and 2 show that the films formed using the emulsified composition of the present invention exhibit excellent ice-breaking and artificial snow-sliding effects. In particular, the film formed using the emulsified composition of Example 2 allowed even small amounts of accumulated snow to slide off within 10 minutes, demonstrating a high snow-prevention effect. Furthermore, it was found that films containing the polymer component (E) exhibited higher scratch resistance.

The emulsifying composition of the present invention can form a film with anti-icing and anti-snowing properties, and can therefore be used in various fields such as coatings for road equipment like signs, markers, and traffic lights in snowy areas, vehicles such as automobiles, airplanes, and trains, headlights, solar panels, power lines, and roofs and windows of buildings.

Claims (7)

An emulsified composition for ice and snow protection containing the following components (A) to (C).
(A) Modified cellulose fibers of component (b) below
(b) Hydrophobic modified cellulose fiber having a type I crystalline structure, wherein one or more modifying compounds selected from the group consisting of polymer compounds and hydrocarbon compounds having cationic groups are bonded to one or more groups selected from the group consisting of anionic groups and hydroxyl groups of an anionic modified cellulose fiber, wherein the polymer compound is an amino-modified silicone, and the hydrocarbon compound having cationic groups is a compound selected from the group consisting of primary amines, secondary amines, tertiary amines and quaternary ammonium compounds. (B) Water (C) An organic compound that is liquid at 25°C and 1 atm, wherein the organic compound is one or more organic compounds selected from the group consisting of ester oils, hydrocarbon oils, silicone oils other than the modifying compounds, ether oils, fats and oils, fluorinated inert liquids and fatty acids. The anti-icing and snow-preventing emulsified composition according to claim 1, wherein the silicone oil other than the modifying compound in component (C) is one or more selected from the group consisting of dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. The anti-ice and anti-snow emulsifying composition according to claim 1 or 2, further comprising the following component (D).
(D) Polyether-modified silicone compound The emulsified composition for ice and snow protection according to claim 3 , further comprising the following component (E).
(E) Polymer compounds other than components (A) and (D) The anti-ice and snow-prevention emulsifying composition according to claim 4, wherein component (E) is a polymer compound containing a (meth)acrylic polymer. A method for producing an anti-icing and anti-snow film, comprising the steps of applying and drying an anti-icing and anti-snow emulsified composition according to any one of claims 1 to 5. A structure in which the anti-ice/snow-prevention emulsified composition according to any one of claims 1 to 5 has dried and formed a coating film.